EP0022279B1 - Method of manufacturing an optically transparent and electroconductive thin-film pattern - Google Patents

Method of manufacturing an optically transparent and electroconductive thin-film pattern Download PDF

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Publication number
EP0022279B1
EP0022279B1 EP80200378A EP80200378A EP0022279B1 EP 0022279 B1 EP0022279 B1 EP 0022279B1 EP 80200378 A EP80200378 A EP 80200378A EP 80200378 A EP80200378 A EP 80200378A EP 0022279 B1 EP0022279 B1 EP 0022279B1
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EP
European Patent Office
Prior art keywords
etching
layer
process according
carrier
acid
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Expired
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EP80200378A
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German (de)
French (fr)
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EP0022279A1 (en
Inventor
Walter Dr.-Phys. Schmidt
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BBC Brown Boveri AG Switzerland
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BBC Brown Boveri AG Switzerland
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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C23/00—Other surface treatment of glass not in the form of fibres or filaments
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K13/00—Etching, surface-brightening or pickling compositions
    • C09K13/04—Etching, surface-brightening or pickling compositions containing an inorganic acid
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F1/00—Etching metallic material by chemical means
    • C23F1/02—Local etching
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1343—Electrodes
    • G02F1/13439—Electrodes characterised by their electrical, optical, physical properties; materials therefor; method of making

Definitions

  • the invention relates to a method for producing an optically transparent and electrically conductive film pattern according to the preamble of claim 1.
  • optically transparent area electrodes are required to expose the dielectric medium between predetermined, electrically controllable parts of the transparent area electrode and a second electrode layer in correspondingly overlapping areas between the area electrode and the second electrode, locally limited fields, z. B. to locally change the optical properties of a liquid crystal layer used as a dielectric, so that a display corresponding to the controlled areas becomes visible through the transparent area electrode.
  • Corresponding carrier plates also called “substrates”, e.g. B. glass plates with transparent area electrode layers or films are usually made in that a coherent thin film made of transparent and electrically conductive material, e.g. B. semiconducting metal oxides, such as In 2 0 3 or / and Sn0 2 , z. B. by evaporation or sputtering in a vacuum and then removed in some areas by etching.
  • the vapor-deposited or sputtered films are relatively easy to etch with acids when fresh, ie not annealed.
  • the film on the carrier plate is covered with a layer of photopolymerizable material by the photoresist or photoresist method, which layer can be polymerized by imagewise exposure in the exposed areas and then removed from the unexposed areas to form the windows of an etching mask. Then the uncovered areas of the film are etched off and then the photoresist layer is removed from the covered areas of the transparent electrode film which remain on the carrier plate.
  • This photoresist etching method according to the preamble of claim 1, as is known for example from DE-A-2 741 440, enables the production of very complex or fine-line area electrodes, but is very expensive or time-consuming.
  • Printing a cover mask before the electrode film is evaporated also leads to problems because the printed cover layer produces so-called edge shadows and can thus impair the definition of the electrode pattern; furthermore, the printed cover layer must first be dried before vapor deposition and removed after vapor deposition, e.g. B. by washing, burning or brushing, which is made even more difficult by the layer formed during evaporation on the covered areas.
  • the object of the present invention is therefore a method for producing an optically transparent and electrically conductive film pattern on a carrier plate, which avoids the manufacturing disadvantages of the photoresist method with unchanged high accuracy and overcomes the difficulties of the known pressure etching method.
  • the object is achieved in a method according to the preamble of claim 1 by the features from the characterizing part of this claim.
  • the areas to be removed by etching of the layer (electrode layer) made of electrically conductive and optically transparent material, usually made of semiconducting metal oxide, such as In 2 0 3 and / or Sn0 2 , previously applied to the mostly transparent carrier layer in a manner known per se, are covered with a Printed mass, e.g. B. according to the known screen printing method, which contains an etchant for the conductive transparent material or metal oxide; the resulting layer-like coating on the areas of the transparent electrode layer to be etched is preferably relatively thin, e.g. B.
  • the transparent electrode layer to be etched is usually comparatively very thin, e.g. B. 0.01 to 0.05 .mu.m, can be obtained with a printed etching layer of the above thickness, a rapid and complete etching of the electrode layer regions to be removed with a mass ("printing paste” or "printing ink”) that only a few percent mineral acid contains, at normal or moderately elevated temperatures and with an etching time of a few seconds or a few minutes.
  • the printed etching layer is then removed with the etching products of the electrode layer, which can be done easily and simply by rinsing.
  • the mass preferably contains a carrier which (a) is inert to the electrode layer, i.e. H. it is not chemically or otherwise modified, (b) is compatible (compatible) or miscible with the etchant, (c) is soluble in suitable solvents, preferably organic solvents, and (d) the composition is suitable for the printing method chosen Viscosity or consistency (no bleeding on the printed substrate) gives.
  • stage B of FIG. 1 a photoresist layer 12 is applied to the conductive layer 11 and dried, i. H. stage B comprises at least two substeps.
  • stage C of e.g. B. 1 the photoresist layer is exposed imagewise through a mask (not shown), so that exposed areas 120 and unexposed areas 121 of the photoresist layer are formed.
  • stage D of FIG. 1 the etching mask 130 formed by “developing” the photoresist layer is shown on the parts of the conductive layer 11 that are not to be etched.
  • the transition from stage C to stage D according to FIG. 1 therefore usually comprises several steps (hardening of the mask regions 120, removal of the window regions 121, possibly cleaning).
  • Step E of FIG. 1 shows the areas 110 of the conductive layer covered with the mask 130 after etching off the uncovered conductive layer areas (111 of step D).
  • Step F of FIG. 1 shows the substrate 10 with the conductive layer regions 110 of the finished pattern after the etching mask regions 130 have been removed.
  • the starting material of the method according to the invention shown in stage A of FIG. 1 corresponds to the starting material of the known method explained in FIG. 1, consists of the substrate or the carrier plate 20 with a continuous layer 21 (conductive layer) applied thereon and is like the starting material of the known method 1 commercially available.
  • steps B, C of FIG. 1 The steps of applying the etching mask made of photoresist (i.e. steps B, C of FIG. 1), which are explained in FIG. 1 and in some cases mostly multi-step, are omitted.
  • a layer 25 printed in a pattern-like manner is applied to the conductive layer 21 of the starting material (stage A) on the conductive layer regions 211 to be removed by etching, while the desired conductive layer regions 210 of the electrode pattern to be produced remain free.
  • stage C of FIG. 2 arises in a very short time; H. the etched areas 251 between the unetched conductive layer areas 210 on the carrier plate 20.
  • the etched areas 251 mostly consist for the most part of the unused portions of the printed etchant mass and from the products of the reaction of etchant and conductive layer material, e.g. B. indium and tin phosphate plus water when using the phosphoric acid preferred according to the invention for many purposes.
  • the product of the last stage of the method according to the invention corresponds to that of the known method, but can be obtained by simply washing off the etched areas 251, for example by immersion in a suitable solvent, of the product from stage C, FIG. 2 will.
  • the type of substrate (20, FIG. 2) or the carrier plate is not critical as long as the substrate is suitable for printing with an etching material layer, i. H. has at least one practically flat surface with a conductive layer applied thereon.
  • Silicate glass is a typical example; quartz glasses or organic glasses are also suitable for the substrate.
  • the part of the substrate provided with the conductive layer is normally an electrical insulator, but removed parts of the substrate can be made of conductive material.
  • a substrate suitable as a carrier plate according to the invention can thus also be a multi-component or composite structure.
  • the material used for the conductive layer (21, FIG. 2) or its thickness and other properties are only important with regard to the end use of the product of the method according to the invention, but not the method itself.
  • oxides of metals which are customary for such conductive layers, such as indium and / or tin
  • oxides of zinc which are doped with antimony oxide and cadmium can also be used.
  • the preferred conductive layer material based on indium oxide is technically available under the trade name ITO. But correspondingly thin metal layers can also be optically transparent or translucent - d. H. have sufficient optical transmission - and can be etched according to the invention.
  • Special pretreatments of the substrate provided with a conductive layer are not required for the method according to the invention or - as for. B. annealing - mostly inappropriate if they change or worsen the etchability of the conductive layer.
  • the usual screen printing is preferred as the printing method for the area-by-layer application of the etching compound layer (25, FIG. 2), because with this printing method also very fine patterns, e.g. B. with line widths of only 0.1 mm, defined printing and can be etched out according to the invention.
  • Suitable screen printing machines are commercially available and the customary, correspondingly fine-meshed printing screens are normally resistant to the etching agents preferred according to the invention or can be used without difficulty against correspondingly resistant screens, e.g. B. from acid-resistant natural or synthetic filaments, such as silk, nylon, polyester, etc., are exchanged.
  • the mask of the printing screen can be produced photolithographically in a conventional manner and of course, like the printing screen itself, should be resistant to the etchant of the mass serving as printing ink.
  • the etchant can also be applied by offset, pad printing and similar methods, as long as the definition of the etching pattern necessary for the respective intended use of the finished product can be achieved.
  • the composition used for printing according to the invention contains the etchant, usually a mineral acid, optionally in a form diluted with water or another solvent for the acid.
  • Phosphoric acid is because of de; good caustic effect and the advantageous performance properties of this acid are preferred, but other normally liquid or water-soluble acids, such as hydrohalic acids, e.g. B. aqueous HCl, halogen oxygen acids, nitric acid, sulfuric acid or strong organic acids, which are capable of forming salts with the conductive layer material.
  • the mass contains an inert carrier in addition to the etchant.
  • the oleophilic components of printing inks known as "binders" or vehicles are suitable for many purposes of the invention, e.g. B. the technically available material for screen printing compositions based on cedar oil.
  • Organic or inorganic oils, optionally with thickeners, are to be mentioned as an example of a suitable class of substances for the inert carrier.
  • the consistency of the etching compound can be liquid to pasty, depending on the type of printing process.
  • the printing composition generally contains 1 to 50% by weight, preferably 3 to 40% by weight, of etchant and inert carrier as the remaining portion.
  • Usual additives for printing compounds can be used, but usually do not bring any particular advantages.
  • the viscosity of the mass can be changed in a controlled manner, e.g. B. for thermally controlled viscosity increase.
  • the etching compound can be polymerized in the course of the etching in order to reduce or switch off the effect of the etchant due to an increasing matrix effect of the carrier in the course of the etching.
  • the removal of the etching layer (251, FIG. 2) after the complete etching through of the areas to be removed (211, FIG. 2) of the conductive layer usually within 1 to 120 seconds, depending on the temperature, by simple washing, e.g. B. in oleophilic vehicles with organic lipophilic technical solvents such as trichlorethylene, gasoline.
  • oleophilic vehicles with organic lipophilic technical solvents such as trichlorethylene, gasoline.
  • hydrophilic carriers of the printed mass is less preferred because this can favor an uncontrolled or unintentional etching of the conductive layer areas (210, FIG. 2) of the pattern to be produced.
  • the substrates with the electrically conductive film pattern obtained by the process according to the invention can be post-treated or used in the same way as the analog products of the photoresist etching process, e.g. B. by annealing or baking, and installation in liquid crystal displays, such as those used for clocks, measuring devices and numerous other purposes.
  • This composition was printed with a conventional screen printing machine to the existing of In 2 0 3/2 Sn0 conductive layer (thickness 25 nm ⁇ 1.25 nm) commercially available carrier plate made of silicate glass.
  • the thickness of the printed mass layer was 20 1 1m ⁇ 5 1 1m. After 5 seconds of etching at 60 ° C., the printed mass was rinsed off with excess amyl acetate and the substrate now provided with a conductive layer pattern was allowed to air dry.
  • the guiding layer was structured according to the configuration of the printing screen with high resolution (defined line widths of 0.1 mm).

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Description

Die Erfindung betrifft ein Verfahren zur Herstellung eines optisch transparenten und elektrisch leitfähigen Filmmusters gemäß dem Oberbegriff des Anspruchs 1.The invention relates to a method for producing an optically transparent and electrically conductive film pattern according to the preamble of claim 1.

Für verschiedene Typen elektrooptischer Anzeigen, z. B. Flüssigkristallanzeigen, werden optisch transparente Bereichselektroden benötigt, um das dielektrische Medium zwischen vorbestimmten, elektrisch ansteuerbaren Teilen der transparenten Bereichselektrode und einer zweiten Elektrodenschicht in entsprechend einander übedeckenden Bereichen zwischen der Bereichselektrode und der zweiten Elektrode örtlich begrenzten Feldern auszusetzen, z. B. um die optischen Eigenschaften einer als Dielektrikum verwendeten Flüssigkristallschicht örtlich zu verändern, so daß eine den angesteuerten Bereichen entsprechende Anzeige durch die transparente Bereichselektrode hindurch sichtbar wird.For different types of electro-optical displays, e.g. B. liquid crystal displays, optically transparent area electrodes are required to expose the dielectric medium between predetermined, electrically controllable parts of the transparent area electrode and a second electrode layer in correspondingly overlapping areas between the area electrode and the second electrode, locally limited fields, z. B. to locally change the optical properties of a liquid crystal layer used as a dielectric, so that a display corresponding to the controlled areas becomes visible through the transparent area electrode.

Entsprechende Trägerplatten, auch »Substrate« genannt, z. B. Glasplatten mit transparenten Bereichselektrodenschichten oder -filmen werden meist dadurchhergestellt, daß auf eine Oberfläche der Trägerplatte ein zusammenhängender dünner Film aus transparentem und elektrisch leitfähgem Material, z. B. halbleitenden Metalloxiden, wie In203 oder/und Sn02, aufgebracht wird, z. B. durch Aufdampfen oder Aufsputtern im Vakuum und dann bereichsweise durch Ätzen entfernt wird. Die aufgedampften oder aufgesputterten Filme sind in frischem, d. h. nicht getempertem Zustand mit Säuren relativ leicht ätzbar; zur lokal begrenzten Ätzung wird der Film auf der Trägerplatte nach dem Photoresist- oder Photolackverfahren mit einer Schicht aus photopolymerisierbarem Material abgedeckt, die durch bildmäßige Belichtung in den belichteten Bereichen polymerisiert und dann an den unbelichteten Bereichen zur Bildung der Fenster einer Ätzmaske entfernt werden kann. Dann werden die nicht abgedeckten Bereiche des Filmes abgeätzt und danach die Photolackschicht von den abgedeckten, auf der Trägerplatte verbleibenden Bereichen des transparenten Elektrodenfilmes entfernt. Dieses Photoresist-Ätzverfahren gemäß dem Oberbegriff des Anspruchs 1, wie es beispielsweise aus der DE-A-2 741 440 bekannt ist, ermöglicht die Herstellung von sehr komplexen bzw. feinstrichigen Bereichselektroden, ist aber sehr kostspielig bzw. zeitraubend.Corresponding carrier plates, also called "substrates", e.g. B. glass plates with transparent area electrode layers or films are usually made in that a coherent thin film made of transparent and electrically conductive material, e.g. B. semiconducting metal oxides, such as In 2 0 3 or / and Sn0 2 , z. B. by evaporation or sputtering in a vacuum and then removed in some areas by etching. The vapor-deposited or sputtered films are relatively easy to etch with acids when fresh, ie not annealed. For locally limited etching, the film on the carrier plate is covered with a layer of photopolymerizable material by the photoresist or photoresist method, which layer can be polymerized by imagewise exposure in the exposed areas and then removed from the unexposed areas to form the windows of an etching mask. Then the uncovered areas of the film are etched off and then the photoresist layer is removed from the covered areas of the transparent electrode film which remain on the carrier plate. This photoresist etching method according to the preamble of claim 1, as is known for example from DE-A-2 741 440, enables the production of very complex or fine-line area electrodes, but is very expensive or time-consuming.

Zur Herstellung von solchen transparenten Bereichseiektroden ist es weiterhin bekannt, das elektrisch leitfähige Material für den transparenten Elektrodenfilm nur bereichsweise auf die entsprechend abgedeckte Trägerplatte aufzudampfen; zum Abdecken der nicht mit Elektrodenfilm zu versehenden Bereiche der Trägerplatte kann auf diese Weise entweder eine Metallmaske aufgelegt oder ein entsprechendes Abdeckmuster aufgedruckt werden (siehe z. B. DE-AS 2322826). Das Abdecken mit einer Metallmaske ist problematisch, weil der erforderliche enge Kontakt zwischen Maske und Trägerplatte sehr schwierig zu erreichen und die Gefahr einer unscharfen Abdeckung mit entsprechend schlechter Definition des aufgedampften Musters sehr groß ist. Auch das Aufdrucken einer Abdeckmaske vor dem Aufdampfen des Elektrodenfilmes führt zu Problemen, weil die aufgedruckte Abdeckschicht sogenannte Randschatten erzeugt und damit die Definition des Elektrodenmusters beeinträchtigen kann; ferner muß die aufgedruckte Abdeckschicht vor dem Aufdampfen zunächst getrocknet und nach dem Aufdampfen entfernt weden, z. B. durch Abwaschen, Abbrennen oder Abbürsten, was durch die beim Aufdampfen auch auf den abgedeckten Bereichen gebildete Schicht noch erschwert wird.For the production of such transparent area electrodes, it is also known to vaporize the electrically conductive material for the transparent electrode film only in regions on the correspondingly covered carrier plate; In order to cover the areas of the carrier plate that are not to be provided with an electrode film, a metal mask can be applied in this way or a corresponding masking pattern can be printed on (see, for example, DE-AS 2322826). Covering with a metal mask is problematic because the required close contact between the mask and the carrier plate is very difficult to achieve and the risk of blurred covering with a correspondingly poor definition of the vapor-deposited pattern is very great. Printing a cover mask before the electrode film is evaporated also leads to problems because the printed cover layer produces so-called edge shadows and can thus impair the definition of the electrode pattern; furthermore, the printed cover layer must first be dried before vapor deposition and removed after vapor deposition, e.g. B. by washing, burning or brushing, which is made even more difficult by the layer formed during evaporation on the covered areas.

Ein anderes, ohne Abdeckung arbeitendes Ätzverfahren für dünne Metallschichten, wie sie für die Herstellung von gewickelten Kondensatoren verwendet werden, ist in der US-PS 2 897 066 beschrieben. Darin werden die durch Ätzen zu entfernenden Bereiche der Metallschicht mit einer Ätzmasse bedruckt. Die Ätzmasse wirkt dann auf die bedruckten Bereiche bis zu ihrer Durchätzung ein. Schließlich werden die von dem Ätzmittel aus der Ätzmasse durch Reaktion mit der Metallschicht gebildeten Produkte zusammen mit den nicht verbrauchten Anteilen der aufgedruckten Ätzmasse in einer Waschvorrichtung mittels Wasser entfernt. Während dieses bekannte Verfahren für die vergleichsweise groben Strukturen der metallischen Kondensatorbeläge mit ihrer großen Schichtdicke unkritisch ist, reicht es für die Genauigkeitsanforderungen, die an die Elektroden von elektrooptischen Anzeigevorrichtungen gestellt werden, bei weitem nicht aus. Insbesondere führt auch der Waschprozeß, bei dem die Wirkung des Ätzmittels wegen des Wassers nicht sofort unterbunden wird, zu Schädigungen der dünnen, optisch transparenten Elektodenschicht.Another uncovered thin metal layer etching process used in the manufacture of wound capacitors is described in U.S. Patent No. 2,897,066. The areas of the metal layer to be removed by etching are printed therein with an etching compound. The etching compound then acts on the printed areas until they are etched through. Finally, the products formed by the etchant from the etching compound by reaction with the metal layer, together with the unused portions of the printed etching compound, are removed in a washing device by means of water. While this known method is not critical for the comparatively coarse structures of the metallic capacitor coatings with their large layer thickness, it is far from sufficient for the accuracy requirements that are placed on the electrodes of electro-optical display devices. In particular, the washing process, in which the action of the etchant is not immediately prevented because of the water, also leads to damage to the thin, optically transparent electrode layer.

Aufgabe der vorliegenden Erfindung ist daher ein Verfahren zur Herstellung eines optisch transparenten und elektrisch leitfähigen Filmmusters auf einer Trägerplatte, welches bei unverändert hoher Genauigkeit die fertigungstechnischen Nachteile des Photoresistverfahrens vermeidet und die Schwierigkeiten des bekannten Druckätzverfahrens überwindet.The object of the present invention is therefore a method for producing an optically transparent and electrically conductive film pattern on a carrier plate, which avoids the manufacturing disadvantages of the photoresist method with unchanged high accuracy and overcomes the difficulties of the known pressure etching method.

Die Aufgabe wird bei einem Verfahren gemäß Oberbegriff des Anspruchs 1 durch die Merkmale aus dem kennzeichnenden Teil dieses Anspruchs gelöst. Die durch Ätzen zu entfernenden Bereiche der in an sich bekannter Weise auf die meist transparente Trägerschicht vorgängig aufgebrachten Schicht (Elektrodenschicht) aus elektrisch leitfähigem und optisch transparentem Material, meist aus halbleitendem Metalloxyd, wie In203 und/oder Sn02, werden mit einer Masse bedruckt, z. B. nach dem an sich bekannten Siebdruckverfahren, die ein Ätzmittel für das leitfähige transparente Material bzw. Metalloxid enthält; der so entstandene schichtförmige Belag auf den zu ätzenden Bereichen der transparenten Elektrodenschicht ist vorzugsweise relativ dünn, z. B. 5 bis 50 11m, und enthält das Ätzmittel, meist eine Mineralsäure, wie Phosphorsäure, vorzugsweise in Mischung mit einem Träger. Da die zu ätzende transparente Elektrodenschicht in der Regel vergleichsweise sehr dünn ist, z. B. 0,01 bis 0,05 um, kann mit einer aufgedruckten Ätzschicht der obengenannten Dicke eine rasche und vollständige Abätzung der zu entfernenden Elektrodenschichtbereiche mit einer Masse (»Druckpaste« bzw. »Druckfarbe«) erhalten werden, die nur einige wenige Prozent Mineralsäure enthält, und zwar bei normalen oder mäßig erhöten Temperaturen und mit einer Ätzdauer von einigen Sekunden oder wenigen Minuten.The object is achieved in a method according to the preamble of claim 1 by the features from the characterizing part of this claim. The areas to be removed by etching of the layer (electrode layer) made of electrically conductive and optically transparent material, usually made of semiconducting metal oxide, such as In 2 0 3 and / or Sn0 2 , previously applied to the mostly transparent carrier layer in a manner known per se, are covered with a Printed mass, e.g. B. according to the known screen printing method, which contains an etchant for the conductive transparent material or metal oxide; the resulting layer-like coating on the areas of the transparent electrode layer to be etched is preferably relatively thin, e.g. B. 5 to 50 1 1m, and contains the etchant, usually a mineral acid such as phosphoric acid, preferably in a mixture with a carrier. Since the transparent electrode layer to be etched is usually comparatively very thin, e.g. B. 0.01 to 0.05 .mu.m, can be obtained with a printed etching layer of the above thickness, a rapid and complete etching of the electrode layer regions to be removed with a mass ("printing paste" or "printing ink") that only a few percent mineral acid contains, at normal or moderately elevated temperatures and with an etching time of a few seconds or a few minutes.

Die aufgedruckte Ätzschicht wird dann mit den Ätzungsprodukten der Elektrodenschicht entfernt, was problemlos und einfach durch Abspülen geschehen kann. Vorzugsweise enthält die Masse einen Träger, der (a) für die Elektrodenschicht inert ist, d. h. diese nicht chemisch oder auf andere Weise verändert, (b) mit dem Ätzmittel verträglich (kompatibel) bzw. mischbar ist, (c) in geeigneten Lösungsmitteln, vorzugsweise organischem Lösungsmittel, löslich ist, und (d) der Masse die für das gewählte Druckverfahren geeignete Viskosität bzw. Konsistenz (kein Verlaufen auf dem damit bedruckten Substrat) verleiht.The printed etching layer is then removed with the etching products of the electrode layer, which can be done easily and simply by rinsing. The mass preferably contains a carrier which (a) is inert to the electrode layer, i.e. H. it is not chemically or otherwise modified, (b) is compatible (compatible) or miscible with the etchant, (c) is soluble in suitable solvents, preferably organic solvents, and (d) the composition is suitable for the printing method chosen Viscosity or consistency (no bleeding on the printed substrate) gives.

Die beigeschlossene Zeichnung dient der Erläuterung der Erfindung und dem Vergleich mit dem Stand der Technik. Es zeigt

  • Fig. 1 eine schematische Darstellung der Stufen des bekannten Photoresist-Ätzverfahrens und
  • Fig. 2 eine schematische Darstellung der Stufen des erfindungsgemäßen Verfahrens. In Fig. 1 zeigt die Stufe A das Substrat bzw. die Trägerschicht 10, z. B. eine 0,2 bis 1,5 mm dicke Glasscheibe, mit einer in üblicher Weise aufgetragenen zusammenhängenden Schicht 11 (Leitschicht) aus transparentem elektrisch leitfähigem Material, z. B. In203, das mit Sn02 dotiert ist. Solche beschichteten Substrate sind kommerziell erhältlich.
The accompanying drawing serves to explain the invention and to compare it with the prior art. It shows
  • Fig. 1 is a schematic representation of the stages of the known photoresist etching process and
  • Fig. 2 is a schematic representation of the stages of the method according to the invention. In FIG. 1, stage A shows the substrate or the carrier layer 10, e.g. B. a 0.2 to 1.5 mm thick glass sheet, with a customarily applied continuous layer 11 (conductive layer) made of transparent electrically conductive material, for. B. In 2 0 3 , which is doped with Sn0 2 . Such coated substrates are commercially available.

Gemäß Stufe B von Fig. 1 wird auf die Leitschicht 11 eine Photolackschicht 12 aufgetragen und getrocknet, d. h. die Stufe B umfaßt mindestens zwei Teilschritte. In Stufe C von z. B. 1 wird die Photolackschicht durch eine (nicht dargestellte) Maske bildmäßig belichtet, so daß belichtete Bereiche 120 und unbelichtete Bereiche 121 der Photolackschicht entstehen. In Stufe D von Fig. 1 ist die durch »Entwickeln« der Photoresistschicht gebildete Ätzmaske 130 auf den nicht zu ätzenden Teilen der Leitschicht 11 dargestellt. Auch der Übergang von Stufe C zu Stufe D gemäß Fig. 1 umfaßt somit meist mehrere Schritte (Härtung der Maskenbereiche 120, Entfernung der Fensterbereiche 121, eventuell Reinigung).According to stage B of FIG. 1, a photoresist layer 12 is applied to the conductive layer 11 and dried, i. H. stage B comprises at least two substeps. In stage C of e.g. B. 1, the photoresist layer is exposed imagewise through a mask (not shown), so that exposed areas 120 and unexposed areas 121 of the photoresist layer are formed. In stage D of FIG. 1, the etching mask 130 formed by “developing” the photoresist layer is shown on the parts of the conductive layer 11 that are not to be etched. The transition from stage C to stage D according to FIG. 1 therefore usually comprises several steps (hardening of the mask regions 120, removal of the window regions 121, possibly cleaning).

Stufe E von Fig. 1 zeigt die mit der Maske 130 abgedeckten Bereiche 110 der Leitschicht nach dem Abätzen der nicht abgedeckten Leitschichtbereiche (111 von Stufe D).Step E of FIG. 1 shows the areas 110 of the conductive layer covered with the mask 130 after etching off the uncovered conductive layer areas (111 of step D).

Stufe F von Fig. 1 zeigt das Substrat 10 mit den Leitschichtbereichen 110 des fertigen Musters nach Entfernen der Ätzmaskenbereiche 130.Step F of FIG. 1 shows the substrate 10 with the conductive layer regions 110 of the finished pattern after the etching mask regions 130 have been removed.

Das in Stufe A von Fig. dargestellte Ausgangsmaterial des erfindungsgemäßen Verfahrens entspricht dem Ausgangsmaterial des in Fig. 1 erläuterten bekannten Verfahrens, besteht aus dem Substrat oder der Trägerplatte 20 mit einer darauf aufgebrachten zusammenhängenden Schicht 21 (Leitschicht) und ist wie das Ausgangsmaterial des bekannten Verfahrens gemäß Fig. 1 kommerziell erhältlich.The starting material of the method according to the invention shown in stage A of FIG. 1 corresponds to the starting material of the known method explained in FIG. 1, consists of the substrate or the carrier plate 20 with a continuous layer 21 (conductive layer) applied thereon and is like the starting material of the known method 1 commercially available.

Die in Fig. 1 erläuterten und zum Teil meist mehrschrittigen Stufen des Auftragens der Ätzmaske aus Photolack (d. h. die Stufen B, C von Fig. 1) entfallen. Statt dessen ist gemäß Stufe B von Fig. erfindungsgemäß auf die Leitschicht 21 des Ausgangsmaterials (Stufe A) eine musterartig aufgedruckte Schicht 25 auf die durch Ätzen zu entfernenden Leitschichtbereiche 211 aufgebracht, während die gewünschten Leitschichtbereiche 210 des herzustellenden Elektrodenmusters freibleiben.The steps of applying the etching mask made of photoresist (i.e. steps B, C of FIG. 1), which are explained in FIG. 1 and in some cases mostly multi-step, are omitted. Instead, according to stage B of FIG. 1, according to the invention, a layer 25 printed in a pattern-like manner is applied to the conductive layer 21 of the starting material (stage A) on the conductive layer regions 211 to be removed by etching, while the desired conductive layer regions 210 of the electrode pattern to be produced remain free.

Ohne besondere zusätzliche Maßnahmen, allenfalls durch leichtes Erwärmen (allgemeiner Bereich von 0°C oder weniger bis etwa 100°C, vorzugsweise 30-60° C) entsteht in sehr kurzer Zeit der in Stufe C von Fig. 2 dargestellte Zustand, d. h. die geätzten Bereiche 251 zwischen den ungeätzten Leitschichtbereichen 210 auf der Trägerplatte 20. Die geätzten Bereiche 251 bestehen meist zum weitaus überwiegenden Teil aus den unverbrauchten Anteilen der aufgedruckten Ätzmittelmasse und aus den Produkten der Reaktion von Ätzmittel und Leitschichtmaterial, z. B. Indium- und Zinnphosphat plus Wasser bei Verwendung der für viele Zwecke erfindungsgemäß bevorzugten Phosphorsäure. Das Produkt der letzten Stufe des erfindungsgemäßen Verfahrens (D, Fig. 2) entspricht demjenigen des bekannten Verfahrens, kann aber durch einfaches Abwaschen der geätzten Bereiche 251, etwa durch Eintauchen in ein geeignetes Lösungsmittel, des Produktes von Stufe C, Fig. 2, erhalten werden.Without special additional measures, at most by gentle heating (general range from 0 ° C. or less to about 100 ° C., preferably 30-60 ° C.), the state shown in stage C of FIG. 2 arises in a very short time; H. the etched areas 251 between the unetched conductive layer areas 210 on the carrier plate 20. The etched areas 251 mostly consist for the most part of the unused portions of the printed etchant mass and from the products of the reaction of etchant and conductive layer material, e.g. B. indium and tin phosphate plus water when using the phosphoric acid preferred according to the invention for many purposes. The product of the last stage of the method according to the invention (D, FIG. 2) corresponds to that of the known method, but can be obtained by simply washing off the etched areas 251, for example by immersion in a suitable solvent, of the product from stage C, FIG. 2 will.

Verschiedene, aus der Erläuterung des Schemas von Fig. 2 ohne weiteres verständliche variable Faktoren des erfindungsgemäßen Verfahrens können vom Fachmann entsprechend dem jeweiligen gegebenen Anwendungszweck angepaßt werden:

  • Zunächst ist das Verfahren auch für andere Anwendungen als die bevorzugte Herstellung von Bereichselektroden von Flüssigkristallanzeigen geeignet, nämlich für alle Zwecke, die bereichsweise oder musterartig aufgetragene Filme aus leitfäigem und vorzugsweise transparentem Material auf einem Substrat erfordern; Beispiele hierfür sind Abdeckgläser hochempfindlicher Meßgeräte.
Various variable factors of the method according to the invention, which are easily understandable from the explanation of the diagram in FIG. 2, can be adapted by the person skilled in the art according to the respective given application:
  • First of all, the method is also suitable for applications other than the preferred production of area electrodes of liquid crystal displays, namely for all purposes which require films made of conductive and preferably transparent material on a substrate which are applied in areas or in patterns; Examples of this are cover glasses of highly sensitive measuring devices.

Weiterhin ist die Art des Substrates (20, Fig. 2) bzw. der Trägerplatte solange unkritisch, als das Substrat für das Bedrucken mit einer Ätzmasseschicht geignet ist, d. h. mindestens eine praktisch ebene Oberfläche mit darauf aufgetragener Leitschicht besitzt. Silikatglas ist ein typisches Beispiel; auch Quarzgläser oder organische Gläser kommen für das Substrat in Betracht. Der mit der Leitschicht versehene Teil des Substrates ist normalerweise ein elektrischer Isolator, doch können entfernte Teile des Substrates aus leitfähigem Material bestehen. Ein erfindungsgemäß als Trägerplatte geeignetes Substrat kann somit auch ein Mehrkomponenten- bzw. Verbundgebilde sein.Furthermore, the type of substrate (20, FIG. 2) or the carrier plate is not critical as long as the substrate is suitable for printing with an etching material layer, i. H. has at least one practically flat surface with a conductive layer applied thereon. Silicate glass is a typical example; quartz glasses or organic glasses are also suitable for the substrate. The part of the substrate provided with the conductive layer is normally an electrical insulator, but removed parts of the substrate can be made of conductive material. A substrate suitable as a carrier plate according to the invention can thus also be a multi-component or composite structure.

Das für die Leitschicht (21, Fig. 2) verwendete Material bzw. dessen Dicke und sonstige Eigenschaften sind nur in bezug auf die Endverwendung des Produktes des erfindungsgemäßen Verfahrens, nicht aber das Verfahren selbst, wesentlich. Anstelle der für solche Leitschichten üblichen halbleitenden Oxide von Metallen, wie Indium oder/und Zinn, kommen auch Oxide von Zink, die mit Antimonoxid dotiert sind, sowie Cadmium in Frage. Das bevorzugte Leitschichtmaterial auf Basis von Indiumoxid ist unter der Handelsbezeichnung ITO technisch erhältlich. Aber auch entsprechend dünne Metallschichten können optisch transparent bzw. transluzent sein - d. h. eine ausreichende optische Transmission haben - und lassen sich erfindungsgemäß ätzen.The material used for the conductive layer (21, FIG. 2) or its thickness and other properties are only important with regard to the end use of the product of the method according to the invention, but not the method itself. Instead of the semiconducting oxides of metals which are customary for such conductive layers, such as indium and / or tin, oxides of zinc which are doped with antimony oxide and cadmium can also be used. The preferred conductive layer material based on indium oxide is technically available under the trade name ITO. But correspondingly thin metal layers can also be optically transparent or translucent - d. H. have sufficient optical transmission - and can be etched according to the invention.

Besondere Vorbehandlungen des mit Leitschicht versehenen Substrates sind für das erfindungsgemäße Verfahren nicht erforderlich bzw. - wie z. B. eine Temperung - meist unzweckmäßig, wenn sie die Ätzbarkeit der Leitschicht verändern bzw. verschlechtern.Special pretreatments of the substrate provided with a conductive layer are not required for the method according to the invention or - as for. B. annealing - mostly inappropriate if they change or worsen the etchability of the conductive layer.

Als Druckverfahren zum bereichsweisen Auftragen der Ätzmasseschicht (25, Fig. 2) wird der übliche Siebdruck (Serigraphie) bevorzugt, weil mit diesem Druckverfahren auch sehr feine Muster, z. B. mit Strichbreiten von nur 0,1 mm, definiert aufgedruckt und erfindungsgemäß ausge- ätzt werden können. Geeignete Siebdruckmaschinen sind im Handel erhältlich und die üblichen, entsprechend feinmaschigen Drucksiebe sind normalerweise gegen die erfindungsgemäß bevorzugten Ätzmittel beständig bzw. können ohne Schwierigkeiten gegen entsprechend beständige Siebe, z. B. aus säurebeständigen natürlichen oder synthetischen Filamenten, wie Seide, Nylon, Polyester usw., ausgetauscht werden.The usual screen printing (serigraphy) is preferred as the printing method for the area-by-layer application of the etching compound layer (25, FIG. 2), because with this printing method also very fine patterns, e.g. B. with line widths of only 0.1 mm, defined printing and can be etched out according to the invention. Suitable screen printing machines are commercially available and the customary, correspondingly fine-meshed printing screens are normally resistant to the etching agents preferred according to the invention or can be used without difficulty against correspondingly resistant screens, e.g. B. from acid-resistant natural or synthetic filaments, such as silk, nylon, polyester, etc., are exchanged.

Die Maske des Drucksiebes kann in an sich üblicher Weise photolithographisch erzeugt werden und soll natürlich wie das Drucksieb selbst gegen das Ätzmittel der als Druckfarbe dienenden Masse beständig sein. Anstatt durch den hier meist bevorzugten Siebdruck kann die Ätzmittelmasse aber auch durch Offset, Tampondruck und dergleichen Methoden aufgetragen werden, solange damit die für den jeweiligen Verwendungszweck des fertigen Produktes nötige Definition des Ätzmusters erzielbar ist.The mask of the printing screen can be produced photolithographically in a conventional manner and of course, like the printing screen itself, should be resistant to the etchant of the mass serving as printing ink. Instead of the mostly preferred screen printing here, the etchant can also be applied by offset, pad printing and similar methods, as long as the definition of the etching pattern necessary for the respective intended use of the finished product can be achieved.

Die erfindungsgemäß für das Aufdrucken verwendete Masse enthält das Ätzmittel, meist eine Mineralsäure, gegebenenfalls in mit Wasser oder anderem Lösungsmittel für die Säure verdünnter Form. Phosphorsäure wird wegen de; guten Ätzwirkung und der vorteilhaften anwendungstechnischen Eigenschaften dieser Säure bevorzugt, doch können auch andere normalerweise flüssige oder aber wasserlösliche Säuren, wie Halogenwasserstoffsäuren, z. B. wäßrige HCI, Halogensauerstoffsäuren, Salpetersäure, Schwefelsäure oder starke organische Säuren, verwendet werden, die mit dem Leitschichtmaterial zur Bildung von Salzen befähigt sind.The composition used for printing according to the invention contains the etchant, usually a mineral acid, optionally in a form diluted with water or another solvent for the acid. Phosphoric acid is because of de; good caustic effect and the advantageous performance properties of this acid are preferred, but other normally liquid or water-soluble acids, such as hydrohalic acids, e.g. B. aqueous HCl, halogen oxygen acids, nitric acid, sulfuric acid or strong organic acids, which are capable of forming salts with the conductive layer material.

Im allgemeinen enthält die Masse wie oben angedeutet außer dem Ätzmittel einen inerten Träger. Die als »Bindemittel« bzw. Vehikel bekannten oleophilen Komponenten von Druckfarben sind für viele Zwecke der Erfindung geeignet, z. B. das für Siebdruckmassen technisch erhältliche Material auf Zedernölbasis. Organische oder anorganische Öle, gegebenenfalls mit Verdickungsmitteln, sind als Beispiel einer geeigneten Stoffklasse für den inerten Träger zu nennen. Die Konsistenz der Ätzmasse kann flüssig bis pastös sein, je nach Art des Druckverfahrens.In general, as indicated above, the mass contains an inert carrier in addition to the etchant. The oleophilic components of printing inks known as "binders" or vehicles are suitable for many purposes of the invention, e.g. B. the technically available material for screen printing compositions based on cedar oil. Organic or inorganic oils, optionally with thickeners, are to be mentioned as an example of a suitable class of substances for the inert carrier. The consistency of the etching compound can be liquid to pasty, depending on the type of printing process.

Im allgemeinen enthält die Druckmasse 1 bis 50 Gew.-%, vorzugsweise 3 bis 40 Gew.-%, Ätzmittel und inerten Träger als restlichen Anteil. Übliche Zusatzstoffe für Druckmassen können verwendet werden, bringen aber meist keine besonderen Vorteile.The printing composition generally contains 1 to 50% by weight, preferably 3 to 40% by weight, of etchant and inert carrier as the remaining portion. Usual additives for printing compounds can be used, but usually do not bring any particular advantages.

Hingegen kann es zweckmäßig sein, wenn sich die Viskosität der Masse kontrolliert verändern läßt, z. B. zur thermisch gesteuerten Viskositätserhöhung. Beispielsweise kann die Ätzmasse im Verlauf des Ätzens polymerisiert werden, um die Wirkung des Ätzmittels durch eine zunehmende Matrixwirkung des Trägers im Verlauf des Ätzens zu vermindern oder auszuschalten.On the other hand, it can be useful if the viscosity of the mass can be changed in a controlled manner, e.g. B. for thermally controlled viscosity increase. For example, the etching compound can be polymerized in the course of the etching in order to reduce or switch off the effect of the etchant due to an increasing matrix effect of the carrier in the course of the etching.

Die Entfernung der Ätzschicht (251, Fig. 2) nach dem je nach Temperatur meist innerhalb von 1 bis 120 sec vollständigen Durchätzen der zu entfernenden Bereiche (211, Fig. 2) der Leitschicht kann durch einfaches Abwaschen, z. B. bei oleophilen Trägern mit organischen lipophilen technischen Lösungsmitteln, wie Trichloräthylen, Benzin, erfolgen. Die Verwendung von Wasser bzw. von mit Wasser mischbaren Lösungsmitteln und dementsprechend die Verwendung hydrophiler Träger der aufgedruckten Masse wird weniger bevorzugt, weil dies eine unkontrollierte bzw. unbeabsichtigte Ätzung der Leitschichtbereiche (210, Fig. 2) des herzustellenden Musters begünstigen kann.The removal of the etching layer (251, FIG. 2) after the complete etching through of the areas to be removed (211, FIG. 2) of the conductive layer, usually within 1 to 120 seconds, depending on the temperature, by simple washing, e.g. B. in oleophilic vehicles with organic lipophilic technical solvents such as trichlorethylene, gasoline. The use of water or of water-miscible solvents and, accordingly, the use of hydrophilic carriers of the printed mass is less preferred because this can favor an uncontrolled or unintentional etching of the conductive layer areas (210, FIG. 2) of the pattern to be produced.

Die nach dem erfindungsgemäßen Verfahren erhaltenen Substrate mit elektrisch leitfähigem Filmmuster können in gleiche Weise nachbehandelt bzw. verwendet werden, wie die analogen Produkte des Photoresist-Ätzverfahrens, z. B. durch Tempern bzw. Einbrennen, und Einbau in Flüssigkristallanzeigen, wie sie für Uhren, Meßgeräte und zahlreiche andere Zwecke verwendet werden.The substrates with the electrically conductive film pattern obtained by the process according to the invention can be post-treated or used in the same way as the analog products of the photoresist etching process, e.g. B. by annealing or baking, and installation in liquid crystal displays, such as those used for clocks, measuring devices and numerous other purposes.

Beispielexample

50 Gewichtsteile ätherisches Öl (Handelsprodukt; Binder für Siebdruck; auf Basis von Zedernölfraktionen) wurden mit 10 Gewichtsteilen konzentrierter Phosphorsäure (H3P04) in einem Labormischer durchmischt, bis eine praktisch homogen erscheinende Masse mit honigähnlicher Konsistenz entstanden war.50 parts by weight of essential oil (commercial product; binder for screen printing; based on cedar oil fractions) were mixed with 10 parts by weight of concentrated phosphoric acid (H 3 P0 4 ) in a laboratory mixer until a practically homogeneous mass with a honey-like consistency was obtained.

Diese Masse wurde mit einer üblichen Siebdruckanlage auf die aus In203/Sn02 bestehende Leitschicht (Dicke 25 nm ± 1,25 nm) handelsüblicher Trägerplättchen aus Silikatglas aufgedruckt. Die Dicke der aufgedruckten Masseschicht betrug 20 11m ± 5 11m. Nach 5 sec Ätzdauer bei 60°C wurde die aufgedruckte Masse mit überschüssigem Amylacetat abgespült und das nunmehr mit Leitschichtmuster versehene Substrat an der Luft trocknen gelassen. Die Leitschicht erwies sich entsprechend der Konfiguration des Drucksiebes mit hoher Auflösung (definierte Strichbreiten von 0,1 mm) strukturiert.This composition was printed with a conventional screen printing machine to the existing of In 2 0 3/2 Sn0 conductive layer (thickness 25 nm ± 1.25 nm) commercially available carrier plate made of silicate glass. The thickness of the printed mass layer was 20 1 1m ± 5 1 1m. After 5 seconds of etching at 60 ° C., the printed mass was rinsed off with excess amyl acetate and the substrate now provided with a conductive layer pattern was allowed to air dry. The guiding layer was structured according to the configuration of the printing screen with high resolution (defined line widths of 0.1 mm).

Bezugszeichenliste:Reference symbol list:

  • 10 Trägerschicht10 carrier layer
  • 11 Leitschicht11 conductive layer
  • 110 Leitschichtbereich des Musters110 pattern area of the pattern
  • 111 Ätzbereich der Leitschicht111 etching area of the conductive layer
  • 12 Photolackschicht12 photoresist layer
  • 120 belichteter Bereich von 12120 exposed area of 12
  • 121 unbelichteter Bereich von 12121 unexposed area of 12
  • 130 Ätzmaske130 etching mask
  • 20 Trägerschicht20 carrier layer
  • 21 Leitschicht21 conductive layer
  • 210 Leitschichtbereich des Musters210 pattern area of the pattern
  • 211 Ätzbereich der Leitschicht211 etching area of the conductive layer
  • 25 Ätzpastendruckschicht25 etching paste printing layer
  • 251 Ätzpastenschicht mit zersetztem Leitschichtmaterial251 etching paste layer with decomposed conductive layer material

Claims (8)

1. Process for preparing an optically transparent and electrically conductive film pattern on a carrier plate (20), in particular for the preparation of electro-optical display plates provided zonally with transparent electrode layers, wherein an optically transparent layer (21) which has been applied to the carrier late (20) and consists of an electrically conductive material, is removed in predetermined zones (211) by an etching treatment with an etch, characterisd in that
- an etching composition (25) comprising the etch and oil-containing carrier which is inert towards the layer (21), is prepared,
- those zones (211) of the optically transparent layer (21) on the carrier plate (20) which are to be removed by etching are printing with the etching composition (25),
- the etching composition (25) acts on the printed zones (211) until these are etched through, and then
- the products formed from the etch by reaction with the transparent layer (21) are, together with the unconsumed portions of the etching composition (25) which has been printed on, removed from the carrier plate (20) by means of an organic solvent.
2. Process according to Patent Claim 1, characterised in that the etching composition (25) is applied by screenprinting to the optically transparent layer (21).
3. Process according to Patent Claim 1 or 2, characterised in that the etch contains an acid which is capable of forming soluble products of the conductive material.
4. Process according to Patent Claim 2 and 3, characterisd in that the oil contained in the carrier is a viscous essential oil.
5. Process according to one of Patent Claims 1 to 4, characterised in that the electrically conductive material (21) consists of at least one semi-conducting metal oxide, for example indium(3) oxide and/or tin(4) oxide.
6. Process according to one of Patent Claim 3 to 5, characterised in that the acid is a mineral acid which is compatible with the carrier, preferably phosphoric acid.
7. Process according to one of Patent Claims 1 to 6, characterisd in that the etching composition (25) acts on the printed zones (211) at temperatures between ambient temperature and 100°C, preferably between 30 and 90° C, in particular at about 60° C.
8. Process according to one of Patent Claims 2 to 7, characterised in that the etch is a water-soluble acid, which is liquid at room temperature, or an aqueous solution of an acid.
EP80200378A 1979-07-04 1980-04-25 Method of manufacturing an optically transparent and electroconductive thin-film pattern Expired EP0022279B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CH622979 1979-07-04
CH6229/79 1979-07-04

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Publication Number Publication Date
EP0022279A1 EP0022279A1 (en) 1981-01-14
EP0022279B1 true EP0022279B1 (en) 1984-03-14

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US (1) US4348255A (en)
EP (1) EP0022279B1 (en)
JP (1) JPS5613789A (en)
DE (2) DE2929589A1 (en)
HK (1) HK82184A (en)

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Publication number Priority date Publication date Assignee Title
DE3047218A1 (en) * 1980-12-15 1982-07-15 Siemens AG, 1000 Berlin und 8000 München Selective etching of indium oxide and/or stannic oxide - by mixt. contg. conc. hydrochloric acid, conc. orthophosphoric acid, and small amt. of hydrogen peroxide
EP0075706A2 (en) * 1981-09-26 1983-04-06 VDO Adolf Schindling AG Electro-optical display element and method of manufacturing electro-optical display elements
EP0075706A3 (en) * 1981-09-26 1984-10-03 Vdo Adolf Schindling Ag Electro-optical display element and method of manufacturing electro-optical display elements
FR2607989A1 (en) * 1986-12-09 1988-06-10 Primat Didier Method and device for optical acquisition of a plane scene defined by the plot, on a reflecting backing, of transparent shapes
EP0285298A1 (en) * 1987-03-20 1988-10-05 Hideomi Koinuma A method of manufacturing a conductive or superconductive thin film
EP0422828A1 (en) * 1989-10-09 1991-04-17 Chisso Corporation Improved film carrier
EP0451608A2 (en) * 1990-04-10 1991-10-16 VEGLA Vereinigte Glaswerke GmbH Electrically heated alarm glass pane
EP0451608A3 (en) * 1990-04-10 1992-02-12 Vegla Vereinigte Glaswerke Gmbh Electrically heated alarmed glass plate

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HK82184A (en) 1984-11-09
DE3066926D1 (en) 1984-04-19
JPS5613789A (en) 1981-02-10
DE2929589A1 (en) 1981-01-22
EP0022279A1 (en) 1981-01-14
US4348255A (en) 1982-09-07

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